Defoamer formulation and methods for making and using same

ABSTRACT

Defoamer compositions are disclosed and methods for making and using same, where the defoamer has universal applicability at low concentrations. The defoamer compositions include between 40 vol. % and about 80 vol. % distilled water (other waters may be used instead), 10 vol. % and about 30 vol. % of silicon anti-foam agent and between about 10 vol. % and about 30 vol. % of active silicon anti-foam agent. The defoamer compositions are used in amount of less than or equal to 200 ppm in all foamed downhole fluid systems.

RELATED APPLICATIONS

This application is a divisional application and claims the benefit ofand priority to U.S. patent application Ser. No. 12/885,102 filed Sep.17, 2010 (17 Sep. 2010).

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of this invention relate to a defoamer for use in recyclablefoamable systems for use in all downhole operations including drilling,fracturing, completion, cementing, stimulating, and/or enhancingoperations, where the defoamer has consistent activity across alldownhole operations making the defoamer universal.

More particularly, embodiments of this invention relate to a universaldefoamer for use in foamable systems for use in all downhole operationincluding drilling, fracturing, completion, cementing, stimulating,and/or enhancing operations, where the defoamer includes a combinationof silicone-based antifoam agents at concentrations with effective andefficient characteristic defoaming potency.

2. Description of the Related Art

Frequently, drilling fluid, fracturing fluid, completion fluid,cementing, stimulating fluid systems are designed to produce foams withsuitable characteristics for specific drilling or related operations.The ability to reuse the systems is always advantageous to curtailchemical usage and handling as well as overall economics of anoperation. Despite the obvious advantages, a great number of drillingsystems cannot be reused or recycled, because of the lack of suitabledefoamer systems that permit foam-defoam and refoam cycles. Though, someknown defoamers permit reuse of fluid systems, nevertheless, they arenot environmentally benign.

In prior art, the primary objective was always to formulate a suitablesystem to meet end use conditions. End use conditions like temperature,pH, salinity, contaminants, base fluid and so on are examples. Once asuitable system has been formulated, recyclability for instance, as muchas it is desirable, is a secondary consideration. Hence, there are manyfluid systems that are for single pass operations, with only few beingrecyclable.

While there are many defoamers and defoaming systems, there is acontinued need in the art for defoamers and defoamer systems that haveconsistent performance properties across all downhole operations and allfoaming fluid systems, especially at low concentrations, ≦200 ppm, whilemaintaining the ability for the foam systems to be refoamed or toundergo a number of foam-defoam-refoam cycles.

SUMMARY OF THE INVENTION

Embodiments of defoamer compositions of this invention include on avolume basis between about 40 vol. % and about 80 vol. % distilled water(other waters may be used instead), between about 10 vol. % and about 30vol. % of silicon anti-foam agent and between about 10 vol. % and about30 vol. % of active silicon anti-foam agent, where the composition isstable at temperatures up to about 450° F. and is effective atconcentration of less than or equal to 500 ppm in all foamed fluids usedin downhole applications. The foamed fluids include foamed drillingfluids, foamed completion fluids, foamed fracturing fluids, foamedstimulating fluids, foaming cements, and/or other foamed fluids used indownhole operations.

Embodiments of methods of using the defoamer compositions of thisinvention include adding an effective amount of a defoamer compositionof this invention to a foamed fluid, where the amount is sufficient toresult in a clean break of the foamed fluid, where the defoamercomposition includes on a volume basis between about 40 vol. % and about80 vol. % distilled water (other waters may be used instead), betweenabout 10 vol. % and about 30 vol. % of silicon anti-foam agent andbetween about 10 vol. % and about 30 vol. % of active silicon anti-foamagent and where the effective amount is an amount of the defoamercomposition of less than or equal to about 500 ppm regardless of thefoamed fluid type and where the defoaming composition is stable attemperatures up to about 450° F. and where the defoamer compositionpermits repeated foam-defoam recycles, generally with the addition ofadditional foaming composition.

DEFINITIONS OF TERM USED IN THE INVENTION

The following definitions are provided in order to aid those skilled inthe art in understanding the detailed description of the presentinvention.

The term “fracturing” refers to the process and methods of breaking downa geological formation, i.e. the rock formation around a well bore, bypumping fluid at very high pressures, in order to increase productionrates from a hydrocarbon reservoir. The fracturing methods of thisinvention use otherwise conventional techniques known in the art.

The term “surfactant” refers to a soluble, or partially soluble compoundthat reduces the surface tension of liquids, or reduces inter-facialtension between two liquids, or a liquid and a solid by congregating andorienting itself at these interfaces.

The term “drilling fluids” refers to any fluid that is used during oiland/or gas well drilling operations.

The term “completion fluids” refers to any fluid that is used in oiland/or gas well completion operations.

The term “production fluids” refers to any fluid that is used in oiland/or gas well production operations.

An under-balanced and/or managed pressure drilling fluid means adrilling fluid having a circulating hydrostatic density (pressure) loweror equal to a formation density (pressure). For example, if a knownformation at 10,000 ft (True Vertical Depth—TVD) has a hydrostaticpressure of 5,000 psi or 9.6 lbm/gal, an under-balanced drilling fluidwould have a hydrostatic pressure less than or equal to 9.6 lbm/gal.Most under-balanced and/or managed pressure drilling fluids include atleast a density reduction additive. Other additive many include acorrosion inhibitor, a pH modifier and a shale inhibitor.

The term “foamable” means a composition that when mixed with a gas formsa stable foam.

The term “gpt” means gallons per thousand gallons.

The term “ppt” means pounds per thousand gallons.

DETAILED DESCRIPTION OF THE INVENTION

The inventors have found that defoamer compositions can be formulatedthat are universally efficient and effective at defoaming a wide varietyof foamed fluid systems used in downhole operations, while refoamabilityis maintained. The inventors have found that the defoamer compositionsof this invention can be used in low concentrations in these foamedfluid systems to fully break the foams. The inventors have also foundthat the defoamer compositions of this invention are environmentallybenign. In certain embodiments, the defoamer compositions of thisinvention include an effective amount of Antifoam B available from 3M ofSt. Paul, Minn., which comprises 60.0 wt. % of water, 7.0-13.0 wt. % ofa polydimethylsiloxane, and optionally 5.0 wt. % of methylcellulose.

For the first time, the inventors have been able to develop a defoamerthat is compatible with all foam systems known to the inventors. Notonly do the defoamer compositions of this invention, defoam a widevariety of fluid systems used in downhole operations, the defoamercompositions allow the foamed fluid system to be reused or to undergofoam-defoam and refoam cycles. Most known defoamers are alcohols,mixture of alcohols, ethers, hydrocarbon, or other combinations thereof.Many of these defoamers are hazardous to the environment, while thedefoamer compositions of this invention may be used without specialhandling and disposal requirements. The defoamer compositions of thisinvention are effective and efficient at low concentrations of less thanor equal to about 200 ppm, while most competitive defoamers areeffective at concentration of greater than or equal to about 2,000 ppm.Therefore, the defoamer compositions of this invention are more costeffective, than other well known defoamers currently used in the market.

The defoamer compositions of this invention have been successfullytested in the field. The defoamer compositions of this invention mayformulated into green chemistry compositions. The inventors have foundthat the defoamer compositions of this invention combine several uniquefeatures that are superior to defoamers described in prior art. Thedefoamer compositions of this invention are thermal stable up to 450°F., are environmentally benign, are robust in their ability to defoamdiverse foaming systems under different operating conditions, whileretaining the usability of foaming systems—maintain the foaming systemsability to undergo repeated foam-defoam-refoam cycles. The defoamercompositions of this invention have effective and efficient defoamingproperties even at low concentrations and are compatible with drillingfluids additives, completion fluid additives, fracturing fluidadditives, cement additives and additives used in other downholeoperations that utilized foaming systems. The defoamer compositions ofthis invention are also more affordable than many other defoaming systemcurrently known. The defoamer composition of this invention permitrepeated foam-defoam cycles, where the number of foam-defoam cycles isat least 2. In other embodiments, the number of foam-defoam cycles is atleast 5. In other embodiments, the number of foam-defoam cycles is atleast 10.

Drilling Fluids

Generally, foamed drilling fluid are used during the drilling of a well.Foamed drilling fluids may be designed for so-called under-balanceddrilling (a hydrostatic pressure of the drilling fluid is lower than thepore pressure of the formation) or managed pressure drilling, where thehydrostatic pressure of the drilling fluid is managed depending on thenature of the material through which drilling is occurring and isgenerally foamed to reduce hydrostatic pressure of the drilling fluidrelative to the formation hydrostatic pressure to reduce fluidpenetration into the formation. The defoamer compositions of thisinvention are designed to defoam such drilling fluids at lowconcentration, even drilling fluids operating at temperatures up to 450°F.

Embodiments of the present invention relate to using the defoamercompositions of this invention to defoam foamed drilling fluids, wherean effective amount of a defoamer composition of this invention is addedto the foamed drilling fluid to break the foam. The defoamingcompositions of this invention include aqueous solutions ofsilicone-based antifoamers. Suitable antifoamers are exemplified byAntifoam B and Antifoam 1410 that are available from Dow Corning. Theeffective amount of the defoaming composition is an amount sufficient tobreak the foam or reduce the foam height to zero or near zero (wherenear means within 5% of zero foam height). In certain embodiments, theeffective amount is less than or equal to about 200 ppm.

Completion Fluids

Embodiments of the present invention relate to defoaming or breakingfoamed completion fluids, where the foamed completion fluids aredefoamed with the addition of an effective amount of a defoamercompositions of this invention, where the effective amount is less thanor equal to about 200 ppm.

Fracturing Fluids

Embodiments of the present invention relate to using the defoamercompositions of this invention to defoam foamed fracturing fluids, wherethe foamed fracturing fluids are defoamed with the addition of aneffective amount of a defoamer compositions of this invention, where theeffective amount is less than or equal to about 200 ppm. For additionalinformation on fracturing fluid components that may be used with thefracturing fluids of this invention the reader is referred to U.S. Pat.Nos. 7,140,433, 7,517,447, 7,268,100, 7,392,847, 7,350,579, 7,712,535,and 7,565,933; and United States Published Applications Nos.20070032693, 20050137114, 20090250659, 20050250666, 20080039345,20060194700, 20070173414, 20070129257, 20080257553, 20090203553,20070173413, 20080318812, 20080287325, 20080314124, 20080269082,20080197085, 20080257554, 20080251252, 20090151959, 20090200033,20090200027, 20100000795, 20100012901, 20090067931, 20080283242,20100077938, 20100122815, and 20090275488. These applications andpatents are incorporated by reference through the operation of the lastparagraph of the specification.

Stimulating Fluids

Embodiments of the present invention relate to using the defoamercompositions of this invention to defoam foamed stimulating fluids,where the foamed stimulating fluids are defoamed with the addition of aneffective amount of a defoamer compositions of this invention, where theeffective amount is less than or equal to about 200 ppm.

Compositional Ranges

In certain embodiments, the defoamer compositions of this inventioninclude on a volume basis between about 40 vol. % and about 80 vol. %distilled water (other waters may be used instead), between about 10vol. % and about 30 vol. % of silicon anti-foam agent and between about10 vol. % and about 30 vol. % of active silicon anti-foam agent. Inother embodiments, the defoamer compositions of this invention includeon a volume bases between about 50 vol. % and about 80 vol. % distilledwater (other waters may be used instead), between about 10 vol. % andabout 25 vol. % of silicon anti-foam agent and between about 10 vol. %and about 25 vol. % of active silicon anti-foam agent. In otherembodiments, defoamer compositions of this invention include on a volumebases between about 60 vol. % and about 80 vol. % distilled water (otherwaters may be used instead), between about 10 vol. % and about 20 vol. %of silicon anti-foam agent and between about 10 vol. % and about 20 vol.% of active silicon anti-foam agent. In other embodiments, defoamercompositions of this invention include on a volume bases between about50 vol. % and about 70 vol. % distilled water (other waters may be usedinstead), between about 15 vol. % and about 25 vol. % of siliconanti-foam agent and between about 15 vol. % and about 25 vol. % ofactive silicon anti-foam agent. In certain embodiments, the siliconanti-foam agent is Antifoam B available from Dow Corning and the activesilicon anti-foam agent is Antifoam 1410 available from Dow Corning. Thedefoaming compositions are a milky white liquids having a pH of about7.03 and a specific gravity of about 0.997.

Foaming Composition Ranges

Generally, the amount of defoaming agent added to defoam the lightenedwell fluids is a vol. % amount sufficient to break the foam. In oneembodiment, the defoaming composition is used in ranges from about 0.05vol. % to about 5 vol. %. In another embodiment, the defoamingcomposition is used in ranges from about 0.1 vol. % to about 2.5 vol. %.In another embodiment, the defoaming composition is used in ranges fromabout 0.1 vol. % to about 1.0 vol. %. In another embodiment, thedefoaming composition is used in ranges from about 0.25 vol. % to about0.5 vol. %. In other embodiments, the defoaming composition is used inan effective amount of less than or equal to 500 ppm. In otherembodiments, the defoaming composition is used in an effective amount ofless than or equal to 400 ppm. In other embodiments, the defoamingcomposition is used in an effective amount of less than or equal to 300ppm. In other embodiments, the defoaming composition is used in aneffective amount of less than or equal to 250 ppm. In other embodiments,the defoaming composition is used in an effective amount of less than orequal to 200 ppm.

Suitable Reagents

Suitable water-based defoaming reagents for use in the defoamercompositions of this invention include, without limitation, a mixture ofsilicone agents that have anti-foam activity, where the mixtures includeat least one polydimethylsioxane and where the defoamer compositions areeffective in amount less than or equal to about 200 ppm and stable attemperatures to 450° F. and is universally applicable to all knownfoaming agents. In certain embodiments, the mixture including Antifoam Band Antifoam 4010.

Suitable Drilling Fluid Components

Suitable aqueous base fluids includes, without limitation, seawater,freshwater, saline water or such makeup system containing up to about30% crude oil.

Suitable foaming agents for use in this invention include, withoutlimitation, any foaming agent suitable for foaming aquesous baseddrilling fluids. Exemplary examples of foaming agents include, withoutlimitation KleanFoam™, DuraFoam™, FMA-100™, TransFoam™ (all availablefrom Weatherford International) or mixture or combinations.

Suitable polymers for use in this invention include, without limitation,any polymer soluble in the aqueous base fluid. Exemplary polymersinclude, without limitation, a polymer comprising units of one or more(one, two, three, four, five, . . . , as many as desired) polymerizablesalts of mono-olefins or di-olefins. Exemplary examples includes,without limitation, natural polymers (starch, hydroxymethyl cellulose,xanthan, guar, etc.) and derivates; co-polymerizable monomers such asacrylates (acrylic acid, methyl acrylate, ethyl acrylate, etc.),methacrylates (methacrylic acid, methyl methacrylate, ethylmethacrylate, etc), 2-acrylamindomethylpropane sulfonic acid,vinylacetate, acrylamide, or the like, provided of course that theresulting polymer is soluble in the water base fluid.

Gases

Suitable gases for foaming the foamable, ionically coupled gelcomposition include, without limitation, nitrogen, carbon dioxide, orany other gas suitable for use in formation fracturing, or mixtures orcombinations thereof.

Corrosion Inhibitors

Suitable corrosion inhibitor for use in this invention include, withoutlimitation: quaternary ammonium salts e.g., chloride, bromides, iodides,dimethylsulfates, diethylsulfates, nitrites, bicarbonates, carbonates,hydroxides, alkoxides, or the like, or mixtures or combinations thereof;salts of nitrogen bases; or mixtures or combinations thereof. Exemplaryquaternary ammonium salts include, without limitation, quaternaryammonium salts from an amine and a quaternarization agent, e.g.,alkylchlorides, alkylbromide, alkyl iodides, alkyl sulfates such asdimethyl sulfate, diethyl sulfate, etc., dihalogenated alkanes such asdichloroethane, dichloropropane, dichloroethyl ether, epichlorohydrinadducts of alcohols, ethoxylates, or the like; or mixtures orcombinations thereof and an amine agent, e.g., alkylpyridines,especially, highly alkylated alkylpyridines, alkyl quinolines, C6 to C24synthetic tertiary amines, amines derived from natural products such ascoconuts, or the like, dialkylsubstituted methyl amines, amines derivedfrom the reaction of fatty acids or oils and polyamines,amidoimidazolines of DETA and fatty acids, imidazolines ofethylenediamine, imidazolines of diaminocyclohexane, imidazolines ofaminoethylethylenediamine, pyrimidine of propane diamine and alkylatedpropene diamine, oxyalkylated mono and polyamines sufficient to convertall labile hydrogen atoms in the amines to oxygen containing groups, orthe like or mixtures or combinations thereof. Exemplary examples ofsalts of nitrogen bases, include, without limitation, salts of nitrogenbases derived from a salt, e.g.: C1 to C8 monocarboxylic acids such asformic acid, acetic acid, propanoic acid, butanoic acid, pentanoic acid,hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid, orthe like; C2 to C12 dicarboxylic acids, C2 to C12 unsaturated carboxylicacids and anhydrides, or the like; polyacids such as diglycolic acid,aspartic acid, citric acid, or the like; hydroxy acids such as lacticacid, itaconic acid, or the like; aryl and hydroxy aryl acids; naturallyor synthetic amino acids; thioacids such as thioglycolic acid (TGA);free acid forms of phosphoric acid derivatives of glycol, ethoxylates,ethoxylated amine, or the like, and aminosulfonic acids; or mixtures orcombinations thereof and an amine, e.g.: high molecular weight fattyacid amines such as cocoamine, tallow amines, or the like; oxyalkylatedfatty acid amines; high molecular weight fatty acid polyamines (di, tri,tetra, or higher); oxyalkylated fatty acid polyamines; amino amides suchas reaction products of carboxylic acid with polyamines where theequivalents of carboxylic acid is less than the equivalents of reactiveamines and oxyalkylated derivatives thereof; fatty acid pyrimidines;monoimidazolines of EDA, DETA or higher ethylene amines, hexamethylenediamine (HMDA), tetramethylenediamine (TMDA), and higher analogsthereof; bisimidazolines, imidazolines of mono and polyorganic acids;oxazolines derived from monoethanol amine and fatty acids or oils, fattyacid ether amines, mono and bis amides of aminoethylpiperazine; GAA andTGA salts of the reaction products of crude tall oil or distilled talloil with diethylene triamine; GAA and TGA salts of reaction products ofdimer acids with mixtures of poly amines such as TMDA, HMDA and1,2-diaminocyclohexane; TGA salt of imidazoline derived from DETA withtall oil fatty acids or soy bean oil, canola oil, or the like; ormixtures or combinations thereof.

Other Additives

The drilling fluids of this invention can also include other additivesas well such as scale inhibitors, carbon dioxide control additives,paraffin control additives, oxygen control additives, or otheradditives.

Scale Control

Suitable additives for Scale Control and useful in the compositions ofthis invention include, without limitation: Chelating agents, e.g., Na⁺,K⁺ or NH₄ ⁺ salts of EDTA; Na, K or NH₄ ⁺ salts of NTA; Na⁺, K⁺ or NH₄ ⁺salts of Erythorbic acid; Na⁺, K⁺ or NH₄ ⁺ salts of thioglycolic acid(TGA); Na⁺, K⁺ or NH₄ ⁺ salts of Hydroxy acetic acid; Na⁺, K⁺ or NH₄ ⁺salts of Citric acid; Na⁺, K⁺ or NH₄ ⁺ salts of Tartaric acid or othersimilar salts or mixtures or combinations thereof. Suitable additivesthat work on threshold effects, sequestrants, include, withoutlimitation: Phosphates, e.g., sodium hexamethylphosphate, linearphosphate salts, salts of polyphosphoric acid, Phosphonates, e.g.,nonionic such as HEDP (hydroxythylidene diphosphoric acid), PBTC(phosphoisobutane, tricarboxylic acid), Amino phosphonates of: MEA(monoethanolamine), NH₃, EDA (ethylene diamine), Bishydroxyethylenediamine, Bisaminoethylether, DETA (diethylenetriamine), HMDA(hexamethylene diamine), Hyper homologues and isomers of HMDA,Polyamines of EDA and DETA, Diglycolamine and homologues, or similarpolyamines or mixtures or combinations thereof; Phosphate esters, e.g.,polyphosphoric acid esters or phosphorus pentoxide (P₂O₅) esters of:alkanol amines such as MEA, DEA, triethanol amine (TEA),Bishydroxyethylethylene diamine; ethoxylated alcohols, glycerin, glycolssuch as EG (ethylene glycol), propylene glycol, butylene glycol,hexylene glycol, trimethylol propane, pentaerythritol, neopentyl glycolor the like; Tris & Tetra hydroxy amines; ethoxylated alkyl phenols(limited use due to toxicity problems), Ethoxylated amines such asmonoamines such as MDEA and higher amines from 2 to 24 carbons atoms,diamines 2 to 24 carbons carbon atoms, or the like; Polymers, e.g.,homopolymers of aspartic acid, soluble homopolymers of acrylic acid,copolymers of acrylic acid and methacrylic acid, terpolymers ofacylates, AMPS, etc., hydrolyzed polyacrylamides, poly malic anhydride(PMA); or the like; or mixtures or combinations thereof.

Carbon Dioxide Neutralization

Suitable additives for CO₂ neutralization and for use in thecompositions of this invention include, without limitation, MEA, DEA,isopropylamine, cyclohexylamine, morpholine, diamines,dimethylaminopropylamine (DMAPA), ethylene diamine, methoxy proplyamine(MOPA), dimethylethanol amine, methyldiethanolamine (MDEA) & oligomers,imidazolines of EDA and homologues and higher adducts, imidazolines ofaminoethylethanolamine (AEEA), aminoethylpiperazine, aminoethylethanolamine, di-isopropanol amine, DOW AMP-90™, Angus AMP-95, dialkylamines(of methyl, ethyl, isopropyl), mono alkylamines (methyl, ethyl,isopropyl), trialkyl amines (methyl, ethyl, isopropyl),bishydroxyethylethylene diamine (THEED), or the like or mixtures orcombinations thereof.

Paraffin Control

Suitable additives for Paraffin Removal, Dispersion, and/or paraffinCrystal Distribution include, without limitation: Cellosolves availablefrom DOW Chemicals Company; Cellosolve acetates; Ketones; Acetate andFormate salts and esters; surfactants composed of ethoxylated orpropoxylated alcohols, alkyl phenols, and/or amines; methylesters suchas coconate, laurate, soyate or other naturally occurring methylestersof fatty acids; sulfonated methylesters such as sulfonated coconate,sulfonated laurate, sulfonated soyate or other sulfonated naturallyoccurring methylesters of fatty acids; low molecular weight quaternaryammonium chlorides of coconut oils soy oils or C₁₀ to C₂₄ amines ormonohalogenated alkyl and aryl chlorides; quanternary ammonium saltscomposed of disubstituted (e.g., dicoco, etc.) and lower molecularweight halogenated alkyl and/or aryl chlorides; gemini quaternary saltsof dialkyl (methyl, ethyl, propyl, mixed, etc.) tertiary amines anddihalogenated ethanes, propanes, etc. or dihalogenated ethers such asdichloroethyl ether (DCEE), or the like; gemini quaternary salts ofalkyl amines or amidopropyl amines, such as cocoamidopropyldimethyl, bisquaternary ammonium salts of DCEE; or mixtures or combinations thereof.Suitable alcohols used in preparation of the surfactants include,without limitation, linear or branched alcohols, specially mixtures ofalcohols reacted with ethylene oxide, propylene oxide or higheralkyleneoxide, where the resulting surfactants have a range of HLBs.Suitable alkylphenols used in preparation of the surfactants include,without limitation, nonylphenol, decylphenol, dodecylphenol or otheralkylphenols where the alkyl group has between about 4 and about 30carbon atoms. Suitable amines used in preparation of the surfactantsinclude, without limitation, ethylene diamine (EDA), diethylenetriamine(DETA), or other polyamines. Exemplary examples include Quadrols,Tetrols, Pentrols available from BASF. Suitable alkanolamines include,without limitation, monoethanolamine (MEA), diethanolamine (DEA),reactions products of MEA and/or DEA with coconut oils and acids.

Oxygen Control

The introduction of water downhole often is accompanied by an increasein the oxygen content of downhole fluids due to oxygen dissolved in theintroduced water. Thus, the materials introduced downhole must work inoxygen environments or must work sufficiently well until the oxygencontent has been depleted by natural reactions. For system that cannottolerate oxygen, then oxygen must be removed or controlled in anymaterial introduced downhole. The problem is exacerbated during thewinter when the injected materials include winterizers such as water,alcohols, glycols, Cellosolves, formates, acetates, or the like andbecause oxygen solubility is higher to a range of about 14-15 ppm invery cold water. Oxygen can also increase corrosion and scaling. In CCT(capillary coiled tubing) applications using dilute solutions, theinjected solutions result in injecting an oxidizing environment (O₂)into a reducing environment (CO₂, H₂S, organic acids, etc.).

Options for controlling oxygen content includes: (1) de-aeration of thefluid prior to downhole injection, (2) addition of normal sulfides toproduct sulfur oxides, but such sulfur oxides can accelerate acid attackon metal surfaces, (3) addition of erythorbates, ascorbates,diethylhydroxyamine or other oxygen reactive compounds that are added tothe fluid prior to downhole injection; and (4) addition of corrosioninhibitors or metal passivation agents such as potassium (alkali) saltsof esters of glycols, polyhydric alcohol ethyloxylates or other similarcorrosion inhibitors. Exemplary examples oxygen and corrosion inhibitingagents include mixtures of tetramethylene diamines, hexamethylenediamines, 1,2-diaminecyclohexane, amine heads, or reaction products ofsuch amines with partial molar equivalents of aldehydes. Other oxygencontrol agents include salicylic and benzoic amides of polyamines, usedespecially in alkaline conditions, short chain acetylene diols orsimilar compounds, phosphate esters, borate glycerols, urea and thioureasalts of bisoxalidines or other compound that either absorb oxygen,react with oxygen or otherwise reduce or eliminate oxygen.

Salt Inhibitors

Suitable salt inhibitors for use in the fluids of this inventioninclude, without limitation, Na Minus-Nitrilotriacetamide available fromClearwater International, LLC of Houston, Tex.

Foam Characteristics

Generally, the foamable fluid systems will produce a foam having a foamheight of at least about 400 mL and a half life of at least about 2minutes. In particular, the produced foam will have a foam heightbetween about least 400 mL and about 800 mL and a half life betweenabout 2 minutes and about 15 minutes or greater depending on theapplication and the exact formulation of the hydrocarbon fluid of thisinvention. The stability or half life and foam height of the producedfoam is controlled by the amount and type of the viscosifying agents inthe composition, by the amount and type of the foaming agents in thecomposition, by the amount of gas and type of gas in the composition, bythe temperature of the composition and by the pressure of thecomposition. Generally, increasing the amount of the viscosifying agentsand/or foaming agents, the foam stability and height can be increase.Generally, the viscosifying agents increase the stability more than thefoam height, while the foaming agents increase the foam height. Ofcourse, the foam height is also directly proportional to the amount andtype of gas dissolved or absorbed in the fluid.

EXPERIMENTS OF THE INVENTION Example 1

This example illustrate the preparation of a deformer composition ofthis invention designated D1.

70 L of distilled water were added to a clean reactor followed byaddition of 15 L of Antifoam B available from Dow Corning. The resultantmixture was mixed thoroughly for 5 minutes. Then, 15 L of Antifoam 1410were added with continued mixing for additional 30 minutes to give thedefoamer composition of this invention designate D1, which is a milkywhite liquid having a pH 7.03 and a specific gravity 0.997.

Properties of D1

D1 of Example 1 is a silicone based composition includes apolydimethylsioxane. D1 is non-hazardous and non-toxic to theenvironment. D1 is effective as a defoamer at low treatingconcentrations between 0.1 wt. % and 2.0 wt. % or as needed. D1 permitsfoam-defoam-refoam cycles or permits all Weatherford (WFT) foamers to berecyclable. D1 is a less expensive defoamer than all other defoameravailable from Weatherford. D1 has a high thermal stability. D1 has beenfound to be stable up to 450° F. in the laboratory as evidenced byabsence of any degradation (precipitation) or discoloration. Foamsdefoamed with D1 have been shown to be refoamable in a refoamability oftest system. Thus, D1 is suitable for use under hostile conditions forconventional systems. D1 is also compatible with Weatherford foamdrilling additives.

Table 1 tabulates the breaking or defoaming characteristics of D1 in aseries of four Weatherford foaming systems: FMA™100, KleanFoam™,DuraFoam™ and TransFoam™.

TABLE 1 Defoamer Properties of D1 Foamer D1 Concentration ConcentrationWater Foamer (%) (%) FH^(a) R^(b) Tap FMA ™ 100 0.5 0.8 0 Yes TapKleanFoam ™ 0.5 0.8 0 Yes Tap DuraFoam ™ 0.5 1.0 0 Yes Tap TransFoam ™ O0.5 1.0 0 Yes ^(a)Foam Height ^(b)Recyclable

The data of Table 1 clearly shows that D1 at levels of 1 wt. % or lessis an effective and efficient defoamer for all four Weatherford foamingsystems: FMA™100, KleanFoam™, DuraFoam™ and TransFoam™. The data isunique in that this single defoamer is capable of defoaming fluidsincluding all three of the Weatherford foaming systems and that thedefoamed fluids are refoamable by adding additional foamer.

Corrosion data is tabulated in Table 2 for a drilling fluid includingD1, OmniFoam™ and corrosion inhibitor CorrFoam™1.

TABLE 2 Compatibility of D1 with Drilling Fluid Additives Test Time CorrID Test Fluid (days) (lbft⁻²yr⁻¹) Piting 1 Tap^(a) + OFHT^(b) (2.0%) +D1 (2.0%) 2 7.427 Heavy 2 Tap^(a) + OF^(c) (2.0%) + D1 2 0.199 Slight(2.0% ) + CF1^(d) (0.5%)^(e) 3 SW^(f) (3.5%) + OF^(c) (2.0%) + D1 22.856 Heavy (2.0%) + CF1^(d) (0.5%)^(e) 4 SW^(f) (3.5%) + OF^(c)(2.0%) + Dl (2.0%) 1 2.562 Medium 5 SW^(f) (3.5%) + OFHT^(b) (2.0%) + D11 0.415 Slight (2.0%) + CF1^(d) (0.2%) 6 SW^(f) (3.5%) + OF^(c) (2.0%) +D1 1 0.791 None (2.0%) + CF1^(d) (0.5%) 7 SW^(f) (3.5%) + OF^(c) (2.0%)D1 1 0.452 Slight (2.0%) + CF1^(d) (0.2%)^(e) ^(a)Elmendorf Tap Water(containing circa 71 ppm Ca²⁺, 21 ppm Na⁺ and 15 ppm Mg²⁺ ions).^(b)OmniFoam ™ HTis a high thermally and saline stable foamer availablefrom Weatherford International ^(c)OmniFoam ™ a saline stable foameravailable from Weatherford International ^(d)CF1 is CorrFoam ™1, acorrosion inhibitor produced by Weatherford International ^(e)pH offluid system adjust to pH 10 ^(f)salt water

The data in Table 2 evidences the compatibility of D1 in a fluidincluding OmniFoam™ and corrosion inhibitor CorrFoam™1. The dataevidenced not only by the acceptable levels of corrosion in the systemscontaining D1, the OmniFoam™ foamer and the CorrFoam™1 inhibitor, butalso the mixtures evidenced an absence of degradation of any of thecomponents at temperatures up to 250° F. Furthermore, minimal amounts ofinhibitor are required for corrosion management in fresh or surprisinglybetter in seawater based fluids. Test IDs 5 and 7 showed that pHadjustment is not needed saving cost of chemical for pH adjustment.

All references cited herein are incorporated by reference. Although theinvention has been disclosed with reference to its preferredembodiments, from reading this description those of skill in the art mayappreciate changes and modification that may be made which do not departfrom the scope and spirit of the invention as described above andclaimed hereafter.

We claim:
 1. A method comprising: adding an effective amount of adefoamer composition to a foamed fluid, where the amount is sufficientto result in a clean break of the foamed fluid, where the defoamercomposition includes, on a volume basis: between about 40 vol. % andabout 80 vol. % distilled water and/or other waters, between about 10vol. % and about 30 vol. % of a silicone anti-foam agent including 60.0wt. % of water, 7.0-13.0 wt. % of a first polydimethylsiloxane, andoptionally 5.0 wt. % of methylcellulose, and between about 10 vol. % andabout 30 vol. % of an active silicone anti-foam agent including 70.0 wt.%-90.0 wt. % water, 7.0 wt. %-13.0 wt. % of a secondpolydimethylsiloxane, 1.0 wt. %-5.0 wt. % hydroxyethyl cellulose, 1.0wt. %-5.0 wt. % of treated amorphous silica, and <1.0 wt. % of C₁₄₋₁₈mono- and di glycerides, where the composition is stable at temperaturesup to about 450° F. and is effective at concentration of less than orequal to 500 ppm in all recyclable foamed fluids including recyclablefoamed drilling fluids, recyclable foamed completion fluids, recyclablefoamed fracturing fluids, recyclable foamed stimulating fluids, andfoaming cements used in downhole applications.
 2. The method of claim 1,wherein the defoamer composition comprises: between about 50 vol. % andabout 80 vol. % distilled water and/or other waters, between about 10vol. % and about 25 vol. % of the silicone anti-foam agent and betweenabout 10 vol. % and about 25 vol. % of the active silicone anti-foamagent.
 3. The method of claim 1, wherein the defoamer compositioncomprises: between about 60 vol. % and about 80 vol. % distilled waterand/or other waters, between about 10 vol. % and about 20 vol. % of thesilicone anti-foam agent and between about 10 vol. % and about 20 vol. %of the active silicone anti-foam agent.
 4. The method of claim 1,wherein the defoamer composition comprises: between about 50 vol. % andabout 70 vol. % distilled water and/or other waters, between about 15vol. % and about 25 vol. % of the silicone anti-foam agent and betweenabout 15 vol. % and about 25 vol. % of the active silicone anti-foamagent.
 5. The method of claim 1, wherein the defoaming composition is amilky white liquids having a pH of about 7.03 and a specific gravity ofabout 0.997.
 6. The method of claim 1, wherein the effectiveconcentration is less than or equal to 400 ppm.
 7. The method of claim1, wherein the effective concentration is less than or equal to 300 ppm.8. The method of claim 1, wherein the effective concentration is lessthan or equal to 250 ppm.
 9. The method of claim 1, wherein theeffective concentration is less than or equal to 200 ppm.
 10. The methodof claim 1, wherein the foamed fluids include foamed drilling fluids,foamed completion fluids, foamed fracturing fluids, foamed stimulatingfluids, foaming cements, and/or other foamed fluids used in downholeoperations.
 11. A method comprising: adding an effective amount of adefoamer composition to a foamed fluid, where the amount is sufficientto result in a clean break of the foamed fluid, where the defoamercomposition includes, on a volume basis: between about 40 vol. % andabout 80 vol. % distilled water and/or other waters, between about 10vol. % and about 30 vol. % of a silicone anti-foam agent including 60.0wt. % of water, 7.0-13.0 wt. % of a first polydimethylsiloxane, and 5.0wt. % of methylcellulose, and between about 10 vol. % and about 30 vol.% of an active silicone anti-foam agent including 70.0 wt. %-90.0 wt. %water, 7.0 wt. %-13.0 wt. % of a second polydimethylsiloxane, 1.0 wt.%-5.0 wt. % hydroxyethyl cellulose, 1.0 wt. %-5.0 wt. % of treatedamorphous silica, and <1.0 wt. % of C₁₄₋₁₈ mono- and di glycerides,where the composition is stable at temperatures up to about 450° F. andis effective at concentration of less than or equal to 500 ppm in allrecyclable foamed fluids including recyclable foamed drilling fluids,recyclable foamed completion fluids, recyclable foamed fracturingfluids, recyclable foamed stimulating fluids, and foaming cements usedin downhole applications.
 12. The method of claim 11, wherein thedefoamer composition comprises: between about 50 vol. % and about 80vol. % distilled water and/or other waters, between about 10 vol. % andabout 25 vol. % of the silicone anti-foam agent and between about 10vol. % and about 25 vol. % of the active silicone anti-foam agent. 13.The method of claim 11, wherein the defoamer composition comprises:between about 60 vol. % and about 80 vol. % distilled water and/or otherwaters, between about 10 vol. % and about 20 vol. % of the siliconeanti-foam agent and between about 10 vol. % and about 20 vol. % of theactive silicone anti-foam agent.
 14. The method of claim 11, wherein thedefoamer composition comprises: between about 50 vol. % and about 70vol. % distilled water and/or other waters, between about 15 vol. % andabout 25 vol. % of the silicone anti-foam agent and between about 15vol. % and about 25 vol. % of the active silicone anti-foam agent. 15.The method of claim 11, wherein the defoaming composition is a milkywhite liquids having a pH of about 7.03 and a specific gravity of about0.997.
 16. The method of claim 11, wherein the effective concentrationis less than or equal to 400 ppm.
 17. The method of claim 11, whereinthe effective concentration is less than or equal to 300 ppm.
 18. Themethod of claim 11, wherein the effective concentration is less than orequal to 250 ppm.
 19. The method of claim 11, wherein the effectiveconcentration is less than or equal to 200 ppm.
 20. The method of claim11, wherein the foamed fluids include foamed drilling fluids, foamedcompletion fluids, foamed fracturing fluids, foamed stimulating fluids,foaming cements, and/or other foamed fluids used in downhole operations.